CN106946819B - Selective process for converting levulinic acid into gamma valerolactone - Google Patents
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Abstract
A process is provided for converting levulinic acid into gamma valerolactone with increased selectivity. The process is based on the recognition of the reaction intermediate 4-hydroxyvaleric acid and its improved conversion.
Description
Technical Field
The present invention relates generally to the conversion of biomass-based feedstocks into components that can be classified as renewable, such as renewable vehicle fuel components. In particular, but not exclusively, the invention relates to the conversion of levulinic acid into gamma valerolactone in a two-step configuration.
Background
Levulinic acid has been identified as a suitable chemical feedstock that can be processed from biomass-derived hexoses. Levulinic acid is converted to Gamma Valerolactone (GVL) via hydrogenation and ring closure to lactones, which is a promising route to make renewable components to be used as fuel components or as such for suitable uses for various syntheses.
The conversion of levulinic acid into gamma valerolactone has been reported in US6617464B 2. Different catalysts capable of performing the hydrogenation and ring closure required for the reaction were investigated and compared. The conversion is carried out at an elevated temperature of 215 ℃.
Another document disclosing a process for converting levulinic acid into gamma valerolactone and further into products such as adipic acid and ammonium adipate is EP2537840B1. The conversion is carried out at 130 ℃ in the presence of at least 0.08% of water relative to the amount of levulinic acid. Although the results show high selectivity, the levulinic acid conversion varies between 51 and 79% and is not satisfactory.
Chalid et al (m. Chalid et al, green polymer precursors from bioglass-based levulinic acid, procedia Chemistry 4 (2012), pages 260-267) have reported a pathway from levulinic acid to various γ -hydroxy-amides used as polymer precursors. One of the steps in the reported process is the biphasic hydrogenation of levulinic acid to gamma valerolactone using a homogeneous, water-soluble Ru- (TPPTS) catalyst. This reaction proceeds through a 4-hydroxyvaleric acid (4-HVA) intermediate product which is not very stable and reacts readily to gamma valerolactone by cyclization. Although levulinic acid is converted rapidly (98%) at 90 ℃, ring closure to gamma valerolactone is not complete after 60 minutes reaction time.
Therefore, there is still a need to control the reaction pathway and further optimize the yield of gamma valerolactone as the final product. It is an object of the present invention to provide a process for the conversion of levulinic acid with better selectivity towards gamma valerolactone. It is a further object to improve the recovery of gamma valerolactone in the process. It is yet another object of the present invention to perform the conversion of levulinic acid under process conditions that minimize hydrogenation by-products.
Disclosure of Invention
The temperatures suggested in the literature provide for a rapid conversion of levulinic acid into gamma valerolactone. The present inventors have now for the first time reported that temperatures above 140 ℃ have produced undesirable by-products under hydrogen-rich conditions. Thus, the almost complete conversion of levulinic acid reported in the prior art does not necessarily provide the best yield of gamma valerolactone, since the process conditions favor even further hydrogenation reactions. Under laboratory conditions, these by-products may not be of interest or may even not be analyzable, but in industrial scale they become relevant and require better selectivity.
According to a first aspect of the present invention there is provided a process for the production of gamma valerolactone wherein levulinic acid is catalytically converted into gamma valerolactone via a reaction pathway by 4-hydroxyvaleric acid as an intermediate. The reaction product is further reacted under conditions to prevent further hydrogenation to convert the remaining 4-hydroxyvaleric acid to gamma valerolactone. This combination of conditions provides selective gamma valerolactone production with reduced by-product formation.
More specifically, provided herein is a method of producing gamma valerolactone, comprising:
converting levulinic acid into 4-hydroxyvaleric acid and gamma valerolactone by catalytic hydrogenation, and
reacting the 4-hydroxypentanoic acid under conditions to prevent further hydrogenation to produce gamma valerolactone.
According to an embodiment of the process of the invention, the choice of reaction conditions contributes to the selectivity. In the catalytic conversion of levulinic acid, i.e. catalytic hydrogenation, the temperature can be chosen to be in the range of from 60 to 120 c, preferably from 80 to 110 c. These conditions have been shown by experimental studies to provide satisfactory conversion of levulinic acid, but at the same time provide very low amounts of unwanted by-products.
The catalytic hydrogenation in the first stage sets minimum requirements on the conditions under which the hydrogenation reaction takes place. However, the present inventors have found that the conditions in the second stage are designed to prevent further hydrogenation reactions from contributing to selectivity and to minimise side reactions associated with over-hydrogenation. Since successful hydrogenation requires optimization and control of the reaction conditions, the transfer to the second stage can be performed simply by removing at least one parameter required for hydrogenation to occur.
The two-step process of the present invention finds its basis in experimental studies on different reaction conditions for each step.
It is essential that the reaction conditions for the conversion of 4-hydroxypentanoic acid to gamma valerolactone prevent hydrogenation. As a reaction step, this is provided by removing at least one parameter associated with the hydrogenation taking place. When all levulinic acid is converted, the reaction conditions in the second stage are chosen to favor this last step, the reaction of 4-hydroxyvaleric acid to gamma valerolactone. At the same time, the formation of hydrogenated by-products from the reaction of 4-hydroxypentanoic acid with gamma-valerolactone which has formed is prevented. According to various embodiments, there are several options to provide such conditions and to perform the removal of the at least one hydrogenation reaction condition. According to one embodiment, the levulinic acid conversion and the 4-hydroxyvaleric acid conversion are carried out in two different reactors, preferably one after the other. The process variables in each reactor can be adjusted to provide optimal conditions first for the hydrogenation reaction and then for the ring closure. According to another embodiment, the two conversions are carried out in one reactor, but the gas atmosphere first comprises hydrogen and, after a set time, is changed to inert gas. According to a third embodiment, the conditions preventing further hydrogenation are provided by reducing the pressure after the first step (levulinic acid conversion).
The conversion of 4-hydroxypentanoic acid to gamma-valerolactone is carried out at a temperature of at least 100 ℃. When no catalyst is used, the temperature is 130 to 200 ℃ and more preferably 150 to 170 ℃. According to another embodiment, the process conditions for reacting the 4-hydroxypentanoic acid to produce gamma valerolactone comprise an acidic catalyst. The temperature at which the 4-hydroxypentanoic acid is reacted to form gamma-valerolactone in the presence of a catalyst is from 100 to 150 ℃ and more preferably from 100 to 120 ℃.
Some embodiments of the present invention provide further benefits, for example, reaction times may be shorter than in prior art processes. Furthermore, less Ru catalyst may be required.
Various embodiments of the present invention will be described with or have been described in connection with only some aspects of the present invention. It will be apparent to the skilled person that any embodiment of one aspect of the invention may be applied to the same and other aspects of the invention.
Detailed Description
Levulinic acid production involves the concept of a biorefinery (biofinery), a facility that integrates biomass conversion processes and equipment to produce fuels, power, and chemicals from biomass.
The chemical composition of biomass strongly depends on its origin. The most abundant carbohydrate in nature is cellulose. Cellulose is a non-branched, water-insoluble polysaccharide consisting of several hundred up to several tens of thousands of glucose units. Levulinic acid can be produced from hexoses, such as glucose, by an acid-catalyzed reaction, producing both 1 mole levulinic acid and formic acid from 1 mole hexose. Levulinic acid can be used as such for different applications, or further reacted to other biological precursors or biological products.
The reaction of levulinic acid to gamma valerolactone proceeds via 4-hydroxyvaleric acid according to the following scheme.
Although hydrogenation and cyclization are given as subsequent reactions, the conversion of levulinic acid actually proceeds readily to gamma valerolactone. In the literature (Chalid), 4-hydroxypentanoic acid is considered as an unstable intermediate. However, in the process of the present invention, the reaction mechanism and the control thereof are considered and the process conditions are adjusted separately. Thus, the process of the invention is also referred to as a two-stage process or two-step process, wherein the different requirements of each step can be optimized.
In the present description, the conversion of levulinic acid into 4-hydroxyvaleric acid and into gamma valerolactone may be referred to as a hydrogenation reaction, a first stage or a first step. However, the mention should not be understood as limiting it only to hydrogenation reactions, since it is well known to the person skilled in the art that the reaction can easily be carried out even to produce gamma valerolactone, provided that the reaction time is sufficiently long. Thus, the reaction product from the levulinic acid conversion comprises both gamma valerolactone and 4-hydroxyvaleric acid, wherein gamma valerolactone is typically the predominant product. According to the process of the invention, the reaction temperature is chosen to be sufficiently low to provide a mixture of both said products. According to an embodiment using two reactors, the reactor in which the hydrogenation takes place is referred to as the hydrogenation reactor or first reactor.
It is generally understood by those skilled in the art that the hydrogenation reaction takes place under reaction conditions which set the requirements. Mainly, a source of hydrogen is required, the temperature and pressure are within a certain range and a catalyst is present. The industrial use of gaseous hydrogen H 2 (g) In that respect Alternatively, hydrogen may be derived from a donor molecule.
In addition, heterogeneous catalysts are commonly used in industrial hydrogenation. Heterogeneous catalysts offer various advantages such as stability of the catalyst, easy separation of the product from the catalyst, a wide range of applicable reaction conditions and a high catalytic ability to hydrogenate the hard-to-reduce functional groups. Heterogeneous commercial catalysts are generally discussed, for example, in catalyst handbooks. Carbonyl hydrogenation is carried out in both gas phase and liquid phase operation, the liquid phase being most common for batch processes involving stirred vessels. Adiabatic fixed bed reactors in series with intermediate cooling or multi-tubular heat exchange reactors may be used for gas phase systems, while trickle adiabatic beds may be used for co-current feeding of liquid carbonyl (carbonyl) feed and hydrogen. It is advantageous to operate the liquid phase reactor at a higher pressure to dissolve H in the reactor 2 And (4) maximizing.
The mechanism by which levulinic acid forms gamma valerolactone via intermediate reactions has been disclosed and studied kinetically. However, side reactions that occur in addition to the 4-HVA to γ -valerolactone reaction have not been studied in detail, since the reaction conditions for converting levulinic acid into γ -valerolactone are typically selected to promote the reaction to proceed completely to form γ -valerolactone. It has been known so far that no separate 4-HVA to gamma valerolactone reaction is required.
In this specification, when referring to the second reaction, second stage or second step, it relates to the formation of gamma valerolactone from the remaining 4-hydroxypentanoic acid present in the reaction mixture after substantially all of the levulinic acid has been converted. According to an embodiment using two reactors, the reactor in which the conditions are selected to prevent hydrogenation to promote the reaction of 4-hydroxypentanoic acid to gamma valerolactone is referred to as the second reactor.
In particular (exceptionally), the second step may be carried out on a fraction (a fraction of) of the reaction products obtained by the hydrogenation reaction. The benefit of this reaction is that most of the reaction products containing gamma valerolactone can bypass the second step and therefore require smaller reaction equipment. However, the required separation or purification is costly.
It is preferred that the reaction product from the first reaction is subjected to the second reaction as such without a separation or purification step. In this case, the reaction product from the first reaction comprises gamma valerolactone as the major component, 4-hydroxyvaleric acid as the minor component, and trace amounts of hydrogenation by-products and levulinic acid starting material. Preferably the amount of each of said trace amounts is less than 1 wt% and preferably less than 0.7 wt% and most preferably less than 0.5 wt% of the total weight of the reaction products from the first reaction. Due to the reaction conditions of the second step, the trace amounts of hydrogenation by-products each amount to less than 1 wt%, preferably less than 0.7 wt%, more preferably less than 0.5 wt% and most preferably less than 0.1 wt% of the total weight of the reaction product also from the second step. For example, after the first step, the amount of 1,4-pentanediol was 0.1 wt% and, within the accuracy of the measurement, appeared to decrease further during the second step of the experiment conducted.
The results of the present invention are unexpected in view of such small amounts of by-products, since the prior art publications do not discuss their effect at all. In laboratory scale they have no correlation (relevance) and in some conditions the concentration may be too low to be easily analysed. However, on an industrial scale, the loss of process yield and the disposal, separation and discharge of undesirable by-products immediately have an impact on the overall economics of production.
Considering the industrial process, it is necessary to convert all levulinic acid into 4-HVA and gamma valerolactone. The person skilled in the art has means to select process control to ensure this conversion. Selecting a lower temperature may require a longer residence time than a higher temperature. However, experiments have shown that temperatures above about 140 ℃ lead to the formation of undesired by-products under hydrogen-rich conditions and thus such conditions are avoided herein. Based on the experimental results, the best temperature range for the hydrogenation reaction is 60-120 deg.C, preferably 80-110 deg.C.
The conversion of levulinic acid into 4-HVA and gamma valerolactone is preferably carried out in the presence of a catalyst. Catalysts suitable for hydrogenation reactions under the conditions of the present invention typically comprise a metal. The hydrogenation metal is preferably selected from metals of group VIII of the periodic table of the elements, more preferably Co, ni, ru, pd and Pt, or combinations thereof. Preferred catalysts include supported Ru-catalysts. The catalyst may be selected from carbon-supported or alumina-supported ruthenium materials. Commercial Ru/C catalysts (with ruthenium contents of about 1-5%) were found to be suitable in the experiments. Typically such catalysts are present in the reaction as pellets or other forms suitable for heterogeneous catalysis in the reactor.
According to the process of the invention, the reaction of 4-HVA to gamma-valerolactone is carried out under conditions which prevent further hydrogenation. In practice, preventing further hydrogenation is most easily accomplished by removing at least one of the hydrogenation reaction conditions required in the first reaction to react the 4-hydroxypentanoic acid in the second reaction to form γ -valerolactone. According to one embodiment, the conditions are provided by carrying out the reaction in a second reactor in which no hydrogenation takes place. Optionally, the temperature in the second reactor may be higher than the temperature in the first reactor, preferably higher than 140 ℃, more preferably from 150 to 200 ℃ and most preferably from 150 to 170 ℃. However, if an acid catalyst is used for the second reaction, the temperature may be from 100 ℃ to 150 ℃, preferably from 100 ℃ to 120 ℃. The pressure is preferably lower than the pressure in the first reactor.
Basically, one way to prevent further hydrogenation reactions is to remove the hydrogenation catalyst (the first stage catalyst). Optionally, according to another embodiment, the reaction of 4-HVA to gamma-valerolactone may be promoted by using another catalyst suitable for the reaction. Such catalyst may be selected from acidic catalysts, such as IER (ion exchange resin) or zeolites. In embodiments where the reaction of 4-HVA to gamma valerolactone (the second reaction) is promoted by the use of a catalyst, the temperature may be lower, ranging from 100 to 150 ℃, preferably from 100 to 120 ℃.
According to one embodiment, the conditions preventing further hydrogenation for the conversion of 4-hydroxypentanoic acid to γ -valerolactone are provided by replacing the hydrogen atmosphere with an inert gas atmosphere. Typically, the inert gas comprises a noble gas or a gas which is rendered inert under the reaction conditions of the process of the present invention. The inert gas may comprise nitrogen, argon and carbon dioxide or any mixture thereof, with nitrogen, carbon dioxide or mixtures thereof being preferred. The atmosphere may be provided, both the reactions are carried out in one reactor or the hydrogenation is carried out in the first reactor and the conversion of 4-hydroxyvaleric acid is carried out in the second reactor. Performing two reactions in one reactor provides benefits in a batch process where the process equipment is simpler due to changing conditions in one reactor. The atmosphere change may be performed together with a temperature change, wherein the temperature of the second step may be higher than the temperature of the first step. Carrying out the first and second reactions in different reactors provides benefits especially when the process is carried out continuously.
The inert gas may be provided to the reactor as a stream. In the case of an inert gas stream, the reaction of 4-hydroxypentanoic acid to γ -valerolactone may be further promoted in said second step by removing water during the reaction. Water is withdrawn from the reaction and from the reactor to shift the reaction equilibrium in the desired direction to form gamma valerolactone. Thereby reducing the final 4-hydroxyvaleric acid that reacts back to levulinic acid.
According to yet another embodiment, the conditions of the second reaction to prevent further hydrogenation are provided by significantly reducing the reactor pressure after said first reaction.
According to another embodiment, the process takes place in a reactor arranged to contain two beds, one bed containing the Ru-catalyst needed for levulinic acid conversion and the other bed containing an acidic catalyst that facilitates the conversion of 4-HVA to gamma valerolactone.
Experiment of the invention
The above description provides non-limiting examples of some embodiments of the invention. It is obvious to a person skilled in the art that the invention is not limited to the details given, but that it may be carried out in other equivalent ways. It may be advantageous to use some of the features of the embodiments disclosed above without using other features. In the experimental part, and in particular in the tables that follow, the following designations are used: levulinic Acid (LA), 4-hydroxypentanoic acid (4-HVA), and Gamma Valerolactone (GVL).
1. Continuous process setup to investigate the influence of different temperatures on the by-product formation during hydrogenation
Experiments were set up to study the effect of temperature on the conversion of levulinic acid to gamma valerolactone, 4-hydroxyvaleric acid and byproducts for almost two months. The constant reactor conditions were: the pressure was 50 bar and the contact time with the catalyst, expressed as WHSV, was 1 h -1 . Levulinic acid was used as feedstock in the experiments to produce gamma valerolactone in a tubular reactor system by hydrogenation over a reduction catalyst (2% Ru/C). The reaction conditions were otherwise kept constant, but the temperature was changed following the following sequence: 140. 150, 130, 150, 110, 90, 150 and 180 ℃.
The formation of 4-hydroxyvaleric acid and various by-products at various reaction temperatures is shown in table 1. The values given represent the gas chromatographic area (GC-area) calculated as the mean value. Here, it is clear that the content of any by-product does not exceed 1% by weight at temperatures of 90-110 ℃. However, at higher temperatures, the sum of the by-products increases and the respective contents are also higher.
More specifically, 1,4-pentanediol and 2-butanol levels are reduced at lower temperatures (90 and 110 ℃). At 180 ℃, the contents of 2-butanol, 2-pentanol, 1-pentanol, 1,4-pentanediol and 2-methyltetrahydrofuran are obviously improved compared with the lower temperature condition.
TABLE 1 examined compounds from LA hydrogenation on Ru/C catalyst at different reaction temperatures.
The results of the experiment show that at lower temperatures the concentration of 4-hydroxypentanoic acid increases, while the concentrations of other by-products decrease. Explained by the favorable selectivity towards gamma valerolactone and 4-hydroxyvaleric acid at low temperatures.
2. Batch experiments using levulinic acid hydrogenation product mixture as feed
The experiment was set up to provide conditions to prevent further hydrogenation, i.e. no hydrogen gas was present. The reaction is carried out under conditions in which the temperature is 150 ℃, the pressure is 2-3 bar and no catalyst is present. The effect of the second step of the two-stage process was investigated with batch experiments, in which the product mixture obtained from the conversion of levulinic acid was used as feed. The feed was obtained from the reaction described in example 1. The product mixture contains mainly gamma valerolactone and the hydrogenated intermediate 4-hydroxyvaleric acid as well as some unreacted levulinic acid. From the Gas Chromatography (GC) analysis results summarized in table 2, it can be concluded: 4-Hydroxypentanoic acid was successfully converted to gamma valerolactone. While effectively limiting the formation of by-products.
TABLE 2 results of the second step of the two-stage process
The increase in gamma valerolactone was significantly higher compared to the decrease in 4-HVA, indicating that gamma valerolactone could also be formed from some other intermediate than 4-HVA. Considering the results given in area%, it can be seen that the increase in area of gamma valerolactone is in the same range as the decrease in area of 4-HVA.
Accordingly, the foregoing description should be considered as merely illustrative of the principles of the present invention, and not in limitation thereof. Accordingly, the scope of the invention is to be limited only by the following claims.
Claims (7)
1. A process for the production of gamma valerolactone in a two stage process comprising:
in a first stage, levulinic acid is converted into 4-hydroxyvaleric acid and gamma valerolactone by catalytic hydrogenation, and
in a second stage, reacting said 4-hydroxypentanoic acid under conditions preventing further hydrogenation and at a temperature of 130-200 ℃ to form gamma-valerolactone,
wherein the conditions to prevent further hydrogenation in the second stage are provided by: i) Performing levulinic acid conversion in a first reactor and 4-hydroxyvaleric acid conversion in a second reactor; ii) reducing the hydrogen pressure after levulinic acid conversion; iii) Carrying out levulinic acid conversion under a hydrogen atmosphere and 4-hydroxyvaleric acid conversion under an inert gas atmosphere; or a combination thereof.
2. The process of claim 1, wherein the conditions under which the 4-hydroxypentanoic acid is reacted to produce gamma valerolactone comprise an acidic catalyst.
3. The process of claim 2, wherein the temperature at which the 4-hydroxypentanoic acid is reacted to form γ -valerolactone is from 130 to 150 ℃.
4. The process of any one of claims 1-3, wherein the reaction conditions for the catalytic hydrogenation of levulinic acid in the first stage comprise at least one of:
a temperature of 60-120 ℃;
a catalyst selected from metals of group VIII of the periodic table of elements or combinations thereof.
5. The process of any of claims 1-3, wherein the reaction conditions for the catalytic hydrogenation of levulinic acid in the first stage comprise at least one of:
a temperature of 80-110 ℃;
a catalyst selected from metals of group VIII of the periodic table of elements or combinations thereof.
6. The process of claim 4 wherein the catalyst used for the catalytic hydrogenation is selected from the group consisting of Co, ni, ru, pd, pt, or combinations thereof.
7. The process of claim 4 wherein the conditions to prevent further hydrogenation in the second stage are provided by: i) Performing levulinic acid conversion in a first reactor and 4-hydroxyvaleric acid conversion in a second reactor; ii) reducing the hydrogen pressure after levulinic acid conversion; iii) Carrying out levulinic acid conversion under a hydrogen atmosphere and 4-hydroxyvaleric acid conversion under an inert gas atmosphere; or a combination thereof.
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| CN101805316A (en) | 2010-04-22 | 2010-08-18 | 复旦大学 | Method for preparing Gamma-valerolactone by using supported iridium catalyst |
| US9523105B2 (en) * | 2010-08-30 | 2016-12-20 | Arzeda Corporation | Fermentation route for the production of levulinic acid, levulinate esters and valerolactone and derivatives thereof |
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| EA025474B1 (en) | 2011-06-21 | 2016-12-30 | ДСМ АйПи АССЕТС Б.В. | Process to produce valerolactone from levulinic acid |
| ES2439869T3 (en) | 2011-06-22 | 2014-01-27 | Dsm Ip Assets B.V. | Continuous production of furfural and levulinic acid |
| CN102558108B (en) | 2011-12-22 | 2014-07-16 | 南开大学 | Process for preparing gamma-valerolactone by utilizing iridium-pincer ligand complex catalyst |
| WO2013102007A1 (en) | 2011-12-28 | 2013-07-04 | E. I. Du Pont De Nemours And Company | Process for the production of furfural |
| CN102617519B (en) | 2012-03-05 | 2014-08-13 | 中国石油大学(华东) | Method for using levulinic acid to prepare gamma-valerolactone by hydrogenation |
| CN102659723B (en) | 2012-04-27 | 2016-02-03 | 北京博能康成科技有限公司 | The method of furfural is prepared with high robust fibre plant agricultural byproducts |
| BR112015026960B1 (en) | 2013-04-27 | 2021-07-27 | The Regents Of The University Of California | METHODS FOR THE PRODUCTION OF REACTIVE INTERMEDIATES FROM BIOMASS AND FOR THE COMBINED SOLUBILIZATION AND CATALYTIC CONVERSION OF BIOMASS |
| WO2015042039A1 (en) | 2013-09-18 | 2015-03-26 | Georgia-Pacific LLC | Method for producing levulinic acid from sludge and lignocellulosic biomass |
| US10556876B2 (en) * | 2015-02-24 | 2020-02-11 | Dsm Ip Assets B.V. | Process for the preparation of gamma valerolactone from levulinic acid |
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2015
- 2015-12-23 FI FI20156006A patent/FI127020B/en active IP Right Grant
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2016
- 2016-12-12 CA CA2951451A patent/CA2951451C/en active Active
- 2016-12-15 ES ES16204213T patent/ES2726286T3/en active Active
- 2016-12-15 EP EP16204213.9A patent/EP3184517B1/en active Active
- 2016-12-22 BR BR102016030289-7A patent/BR102016030289B1/en not_active IP Right Cessation
- 2016-12-22 US US15/388,924 patent/US9914714B2/en active Active
- 2016-12-23 CN CN201611204871.0A patent/CN106946819B/en active Active
Also Published As
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|---|---|
| FI20156006A (en) | 2017-06-24 |
| ES2726286T3 (en) | 2019-10-03 |
| EP3184517B1 (en) | 2019-03-27 |
| US20170183321A1 (en) | 2017-06-29 |
| CA2951451A1 (en) | 2017-06-23 |
| BR102016030289B1 (en) | 2021-04-27 |
| FI127020B (en) | 2017-09-29 |
| CA2951451C (en) | 2022-09-06 |
| EP3184517A1 (en) | 2017-06-28 |
| US9914714B2 (en) | 2018-03-13 |
| BR102016030289A2 (en) | 2017-06-27 |
| CN106946819A (en) | 2017-07-14 |
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